Aqueous, gel laundry detergent composition

ABSTRACT

The present invention relates to stable, aqueous heavy duty gel laundry detergent compositions comprising anionic surfactants, fatty acids, and detersive amines. The anionic surfactant component comprises alkyl ethoxylated sulfates and fatty acids.

RELATED APPLICATIONS

This application is a 371 of PCT/US98/15281 filed Jul. 23, 1998 whichclaims priority under 119(e) to U.S. Serial No. 60/054,099 filed Jul.29, 1997.

TECHNICAL FIELD

The present invention relates to stable, aqueous heavy duty gel laundrydetergent compositions comprising anionic surfactants, fatty acids, andspecially selected agents to provide exceptional cleaning benefits. Theanionic surfactant component comprises alkyl sulfates and alkylethoxylated sulfates.

BACKGROUND OF THE INVENTION

The art is replete with examples of laundry detergent compositions whichhave good cleaning properties. Although many of these are liquids, theformulation of gel detergent compositions present numerous problems tothe formulator, including high viscosity at pouring shear rate,instability during storage, unacceptable grease cleaning, andundesirable appearance.

Attempts to formulate gel laundry detergent compositions in the pasthave included the use of clays or polymers which act to form a shearthinning composition. While these compositions are gels, many have beenfound to have poor physical product characteristics, including phasesplit.

It has now been found that aqueous, heavy duty gel detergentcompositions containing certain anionic surfactants and fatty acidsurfactants provide excellent cleaning performance and attractiveproduct characteristics, i.e., are structured, phase stable, and have arheology which allows for easy pouring from the product container.

Without being limited by theory, it is believed that these novelcompositions have an internal structure which comprises a planarlamellar phase. The presence of such a phase in detergent compositionsmay be determined by optical or electron microscopy.

SUMMARY OF THE INVENTION

It is an object of the invention herein to provide an aqueous heavy dutygel laundry detergent composition which provides excellent cleaning anda desirable rheology.

The present invention encompasses a heavy duty gel laundry detergentcompositions comprising, by weight of the composition:

a) from about 15% to about 40% of an anionic surfactant component whichcomprises, by weight of the composition:

(i) from about 5% to about 25% of alkyl polyethoxylate sulfates whereinthe alkyl group contains from about 10 to about 22 carbon atoms and thepolyethoxylate chain contains from 0.5 to about 15, preferably from 0.5to about 5, more preferably from 0.5 to about 4, ethylene oxidemoieties; and

(ii) from about 5% to about 20% of fatty acids; and

b) and one or more of the following ingredients: detersive amine,modified polyamine, polyamide-polyamine, polyethoxylated-polyaminepolymers, quaternary ammonium surfactants, suitable electrolyte or acidequivalents thereof, and mixtures thereof.

The compositions herein may further contain one or more additionaldetersive additives selected from the group consisting of non-citratebuilders, optical brighteners, soil release polymers, dye transferinhibitors, polymeric dispersing agents, enzymes, suds suppressers,dyes, perfumes, colorants, filler salts, hydrotropes, antiredepositionagents, antifading agent, dye fixative agents, prill/fuzzing reducingagents, and mixtures thereof.

The compositions herein have a viscosity at 20 s⁻¹ shear rate of fromabout 100 cp to about 4,000 cp, preferably from about 300 cp to about3,000 cp, more preferably from about 500 cp to about 2,000 cp and arestable upon storage.

All percentages, ratios and proportions herein are by weight, unlessotherwise specified. All temperatures are in degrees Celsius (°C.)unless otherwise specified. All documents cited are in relevant part,incorporated herein by reference.

DETAILED DESCRIPTION OF THE INVENTION

In accordance with the present invention, it has now been found that astable, aqueous heavy duty gel detergent composition is surprisinglyformed when certain anionic surfactants and fatty acid surfactants arecombined in relative proportions specified hereinafter.

The compositions herein are structured and have a specific rheology. Therheology can be modeled by the following formula:

η=η_(O) +Kγ ^((n−1))

where η is the viscosity of the liquid at a given shear rate, η_(O) isthe viscosity at infinite shear rate, γis the shear rate, n is the shearrate index, and K is the consistency index. As used herein, the term“structured” indicates a heavy duty liquid composition having a liquidcrystalline lamellar phase and an infinite shear viscosity (ηO) valuebetween 0 and about 3,000 cp (centipoise), a shear index (n) value ofless than about 0.6, a consistency index value, K, of above about 1,000,and a viscosity (η) measured at 20 s⁻¹ of less than about 10,000 cp,preferably less than about 5,000 cp. Under low stress levels, a “zeroshear” viscosity is above about 100,000 cp wherein “zero shear” is meanta shear rate of 0.001 s⁻¹ or less. The yield value of the compositionsherein, obtained by plotting viscosity versus stress, is larger than 0.2Pa. These rheology parameters can be measured with any commerciallyavailable rheometer, such as the Carrimed CSL 100 model.

The compositions herein are clear or translucent, i.e. not opaque.

Electrolytes

Without being limited by theory, it is believed that the presence ofelectrolytes acts to control the viscosity of the gel compositions.Thus, the gel nature of the compositions herein are affected by thechoice of surfactants and by the amount of electrolytes present. Inpreferred embodiments herein, the compositions will further comprisefrom 0% to about 10%, more preferably from about 1% to about 8%, evenmore preferably from about 2% to about 6%, of a suitable electrolyte oracid equivalent thereof. Sodium citrate is a highly preferredelectrolyte for use herein.

The compositions herein may optionally contain from about 0% to about10%, by weight, of solvents and hydrotropes. Without being limited bytheory, it is believed that the presence of solvents and hydrotropes canaffect the structured versus isotropic nature of the compositions; By“solvent” is meant the commonly used solvents in the detergent industry,including alkyl monoalcohol, di-, and tri-alcohols, ethylene glycol,propylene glycol, propanediol, ethanediol, glycerine, etc. By“hydrotrope” is meant the commonly used hydrotropes in the detergentindustry, including short chain surfactants that help solubilize othersurfactants. Other examples of hydrotropes include cumene, xylene, ortoluene sulfonate, urea, C₈ or shorter chain alkyl carboxylates, and C₈or shorter chain alkyl sulfate and ethoxylated sulfates.

Modified Polyamine

The compositions herein may comprise at least about 0.05%, preferablyfrom about 0.05% to about 3%, by weight, of a water-soluble ordispersible, modified polyamine agent, said agent comprising a polyaminebackbone corresponding to the formula:

wherein each R¹ is independently C₂-C₅ alkylene, alkenylene or arylene;each R² is independently H, or a moiety of formula OH[(CH₂)_(x)O]_(n),wherein x is from about 1 to about 8 and n is from about 10 to about 50;w is 0 or 1; x+y+z is from about 5 to about 30; and B represents acontinuation of this structure by branching; and wherein said polyaminebefore alkylation has an average molecular weight of from about 300 toabout 1,200.

In preferred embodiments, R¹ is C₂-C₄ alkylene, more preferablyethylene; R² is OH[CH₂CH₂O]_(n), wherein n is from about 15 to about 30,more preferably n is about 20. The average Molecular Weight of thepolyamine before alkylation is from about 300 to about 1200, morepreferably from about 500 to about 900, still more preferably from about600 to about 700, even more preferably from about 600 to about 650.

In another preferred embodiment, R¹ is C₂-C₄ alkylene, more preferablyethylene; R² is OH[CH₂CH₂O]_(n), wherein n is from about 10 to about 20,more preferably n is about 15. The average Molecular Weight of thepolyamine before alkylation is from about 100 to about 300, morepreferably from about 150 to about 250, even more preferably from about180 to about 200.

Polyamide-Polyamines

The polyamide-polyamines useful herein will generally comprise fromabout 0.1% to 8% by the weight of the composition. More preferably, suchpolyamide-polyamine materials will comprise from about 0.5% to 4% byweight of the compositions herein. Most preferably, thesepolyamide-polyamines will comprise from about 1% to 3% by weight of thecomposition.

The polyamide-polyamine materials used in this invention are those whichhave repeating, substituted amido-amine units which correspond to thegeneral Structural Formula No. I as follows:

Structural Formula No.I

In Structural Formula No. I, R₁, R₂ and R₅ are each independently C₁₋₄alkylene, C₁₋₄ alkarylene or arylene. It is also possible to eliminateR₁ entirely so that the polyamide-polyamine is derived from oxalic acid.

Also in Structural Formula No. I, R₃ is H, epichlorohydrin, anazetidinium group, an epoxypropyl group or a dimethylaminohydroxypropylgroup, and R₄ can be H, C₁₋₄ alkyl, C₁₋₄ alkaryl, or aryl. R₄ may alsobe any of the foregoing groups condensed with C₁₋₄ alkylene oxide.

R₁ is preferably butylene, and R₂ and R₅ are preferably ethylene. R₃ ispreferably epichlorohydrin. R4 is preferably H.

The polyamide-polyamine materials useful herein can be prepared byreacting polyamines such as diethylenetriamine, triethylenetetraamine,tetraethylenepentamine or dipropylenetriamine with C₂-C₁₂ dicarboxylicacids such as oxalic, succinic, glutaric, adipic and diglycolic acids.Such materials may then be further derivatized by reaction with, forexample, epichlorohydrin. Preparation of such materials is described ingreater detail in Keim, U.S. Pat. No. 2,296,116, Issued Feb. 23, 1960;Keim, U.S. Pat. No. 2,296,154, Issued Feb. 23, 1960 and Keim, U.S. Pat.No. 3,332,901, Issued Jul. 25, 1967.

The polyamide-polyamine agents preferred for use herein are commerciallymarketed by Hercules, Inc. under the tradename Kymene®. Especiallyuseful are Kymene 557H® and Kymene 557LX® which are epichlorohydrinadducts of polyamide-polyamines which are the reaction products ofdiethylenetriamine and adipic acid. Other suitable materials are thosemarketed by Hercules under the tradenames Reten® and Delsette®, and bySandoz under the tradename Cartaretin®. These polyamide-polyaminematerials are marketed in the form of aqueous suspensions of thepolymeric material containing, for example, about 12.5% by weight ofsolids.

Detersive Amine

Suitable amine surfactants for use herein include detersive aminesaccording to the formula:

wherein R₁ is a C₆-C₁₂ alkyl group; n is from about 2 to about 4, X is abridging group which is selected from NH, CONH, COO, or O or X can beabsent; and R₃ and R₄ are individually selected from H, C₁-C₄ alkyl, or(CH₂—CH₂—O(R₅)) wherein R₅ is H or methyl.

Preferred amines include the following:

wherein R₁ is a C₆-C₁₂ alkyl group and R₅ is H or CH_(3.)

In a highly preferred embodiment, the amine is described by the formula:

R₁—C(O)—NH—(CH₂)₃—N(CH₃)₂

wherein R₁ is C₈-C₁₂ alkyl.

Particularly preferred amines include those selected from the groupconsisting of octyl amine, hexyl amine, decyl amine, dodecyl amine,C₈-C₁₂ bis(hydroxyethyl)amine, C₈-C₁₂ bis(hydroxyisopropyl)amine, andC₈-C₁₂ amido-propyl dimethyl amine, and mixtures.

If utilized the detersive amines comprise from about 0.1% to about 10%,preferably from about 0.5% to about 5%, by weight of the composition.

Quaternary Ammonium Surfactants—from about 1% to about 6% of aquaternary ammonium surfactant having the formula

wherein R₁ and R₂ are individually selected from the group consisting ofC₁-C₄ alkyl, C₁-C₄ hydroxy alkyl, benzyl, and —(C₂H₄O )_(x)H where x hasa value from about 2 to about 5; X is an anion; and (1) R₃ and R₄ areeach a C₆-C₁₄ alkyl or (2) R₃ is a C₆-C₁₈ alkyl, and R₄ is selected fromthe group consisting of C₁-C₁₀ alkyl, C₁-C₁₀ hydroxy alkyl, benzyl, and—(C₂H₄O )_(x)H where x has a value from 2 to 5;

Preferred quaternary ammonium surfactants are the chloride, bromide, andmethylsulfate salts. Examples of preferred mono-long chain alkylquaternary ammonium surfactants are those wherein R₁, R₂, and R₄ areeach methyl and R₃ is a C₈-C₁₆ alkyl; or wherein R₃ is C₈₋₁₈ alkyl andR₁, R₂, and R₄ are selected from methyl and hydroxy-alkyl moieties.Lauryl trimethyl ammonium chloride, myristyl trimethyl ammoniumchloride, palmityl trimethyl ammonium chloride, coconuttrimethylammonium chloride, coconut trimethylammonium methylsulfate,coconut dimethyl-monohydroxyethyl-ammonium chloride, coconutdimethyl-monohydroxyethylammonium methylsulfate, steryldimethyl-monohydroxy-ethylammonium chloride, steryldimethylmonohydroxy-ethylammonium methylsulfate, di-C₁₂-C₁₄ alkyldimethyl ammonium chloride, and mixtures thereof are particularlypreferred. ADOGEN 412™, a lauryl trimethyl ammonium chloridecommercially available from Witco, is also preferred. Even more highlypreferred are the lauryl trimethyl ammonium chloride and myristyltrimethyl ammonium chloride.

Alkoxylated quaternary ammonium (AQA) surfactants useful in the presentinvention are of the general formula:

wherein R¹ is an alkyl or alkenyl moiety containing from about 8 toabout 18 carbon atoms, preferably 10 to about 16 carbon atoms, mostpreferably from about 10 to about 14 carbon atoms; R² and R^(3′)are eachindependently alkyl groups containing from one to about three carbonatoms, preferably methyl; R³ and R⁴ can vary independently and areselected from hydrogen preferred), methyl and ethyl, X⁻ is an anion suchas chloride, bromide, methylsulfate, sulfate, or the like, to provideelectrical neutrality; A is selected from C₁-C₄ alkoxy, especiallyethoxy (i.e., —CH₂CH₂O—), propoxy, butoxy and mixtures thereof; and forformula I, p is from 2 to about 30, preferably 2 to about 15, mostpreferably 2 to about 8; and for formula II, p is from 1 to about 30,preferably 1 to about 4 and q is from 1 to about 30, preferably 1 toabout 4, and most preferably both p and q are 1.

Other quaternary surfactants include the ammonium surfactants such asalkyldimethylammonium halogenides, and those surfactants having theformula:

[R²(OR³)_(y)][R⁴(OR³)_(y)]₂R⁵N⁺X⁻

wherein R² is an alkyl or alkyl benzyl group having from about 8 toabout 18 carbon atoms in the alkyl chain, each R³ is selected from thegroup consisting of —CH₂CH₂—, —CH₂CH(CH₃)—, —CH₂CH(CH₂OH)—, —CH₂CH₂CH₂—,and mixtures thereof; each R⁴ is selected from the group consisting ofC₁-C₄ alkyl, C₁-C₄ hydroxyalkyl, benzyl, ring structures formed byjoining the two R⁴ groups, —CH₂CHOHCHOHCOR⁶CHOH—CH₂OH wherein R⁶ is anyhexose or hexose polymer having a molecular weight less than about 1000,and hydrogen when y is not O; R⁵ is the same as R⁴ or is an alkyl chainwherein the total number of carbon atoms of R² plus R⁵ is not more thanabout 18; each y is from 0 to about 10 and the sum of the y values isfrom 0 to about 15; and X is any compatible anion.

Polyethoxylated-Polyamine Polymers

Another polymer dispersant form use herein includespolyethoxyated-polyamine polymers (PPP). The preferredpolyethoxylated-polyamines useful herein are generallypolyalkyleneamines (PAA's), polyalkyleneimines (PAI's), preferablypolyethyleneamine (PEA's), polyethyleneimines (PEI's). A commonpolyalkyleneamine (PAA) is tetrabutylenepentamine. PEA's are obtained byreactions involving ammonia and ethylene dichloride, followed byfractional distillation. The common PEA's obtained aretriethylenetetramine (TETA) and teraethylenepentamine (TEPA). Above thepentamines, i.e., the hexamines, heptamines, octamines and possiblynonamines, the cogenerically derived mixture does not appear to separateby distillation and can include other materials such as cyclic aminesand particularly piperazines. There can also be present cyclic amineswith side chains in which nitrogen atoms appear. See U.S. Pat. No.2,792,372, Dickinson, issued May 14, 1957, which describes thepreparation of PEA's.

Polyethoxylated polyamines can be prepared, for example, by polymerizingethyleneimine in the presence of a catalyst such as carbon dioxide,sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid,acetic acid, etc. Specific methods for preparing these polyaminebackbones are disclosed in U.S. Pat. No. 2,182,306, Ulrich et al.,issued Dec. 5, 1939; U.S. Pat. No. 3,033,746, Mayle et al., issued May8, 1962; U.S. Pat. No. 2,208,095, Esselmann et al., issued Jul. 16,1940; U.S. Pat. No. 2,806,839, Crowther, issued Sep. 17, 1957; and U.S.Pat. No. 2,553,696, Wilson, issued May 21, 1951

Optionally, but preferred polyethoxyated-polyamine polymers useful forthis invention are alkoxylated quaternary diamines of the generalformula:

where R is selected from linear or branched C₂-C₁₂ alkylene, C₃-C₁₂hydroxyalkylene, C₄-C₁₂ dihydroxyalkylene, C₈-C₁₂ dialkylarylene,[(CH₂CH₂O)_(q)CH₂CH₂]— and —CH₂CH(OH)CH₂O—(CH₂CH₂O)_(q)CH₂CH(OH)CH₂]—where q is from about 1 to about 100. Each R₁ is independently selectedfrom C₁-C₄ alkyl, C₇-C₁₂ alkylaryl, or A. A is of the formula:

where R₃ is selected from H or C₁-C₃ alkyl, n is from about 5 to about100, and B is selected from H, C₁-C₄ alkyl, acetyl, or benzoyl; X is awater soluble anion.

In preferred embodiments, R is selected from C₄ to C₈ alkylene, R₁ isselected from C₁-C₂ alkyl or C₂-C₃ hydroxyalkyl, and A is:

where R₃ is selected from H or methyl, and n is from about 10 to about50.

In another preferred embodiment R is linear or branched C₆, R₁ ismethyl, R₃ is H, and n is from about 20 to about 50.

Additional alkoxylated quaternary polyamine dispersants which can beused in the present invention are of the general formula:

where R is selected from linear or branched C₂-C₁₂ alkylene, C₃-C₁₂hydroxyalkylene, C₄-C₁₂ dihydroxyalkylene, C₈-C₁₂ dialkylarylene,[(CH₂CH₂O)_(q)CH₂CH₂]— and —CH₂CH(OH)CH₂O—(CH₂CH₂O)_(q)CH₂CH(OH)CH₂]—where q is from about 1 to about 100. If present, Each R₁ isindependently selected from C₁-C₄ alkyl, C₇-C₁₂ alkylaryl, or A. R₁ maybe absent on some nitrogens; however, at least three nitrogens must bequaternized.

A is of the formula:

where R₃ is selected from H or C₁-C₃ alkyl, n is from about 5 to about100 and B is selected from H, C₁-C₄ alkyl, acetyl, or benzoyl; m is fromabout 0 to about 4, and X is a water soluble anion.

In preferred embodiments, R is selected from C₄ to C₈ alkylene, R₁ isselected from C₁-C₂ alkyl or C₂-C₃ hydroxyalkyl, and A is:

where R₃ is selected from H or methyl, and n is from about 10 to about50; and m is 1.

In another preferred embodiment R is linear or branched C₆, R₁ ismethyl, R₃ is H, and n is from about 20 to about 50, and m is 1.

The levels of these polyethoxyated-polyamine polymers used can rangefrom about 0.1% to about 10%, typically from about 0.4% to about 5%, byweight. These polyethoxyated-polyamine polymers can be synthesizedfollowing the methods outline in U.S. Pat. No. 4,664,848, or other waysknown to those skilled in the art.

Anionic Surfactant

The anionic surfactant component contains alkyl polyethoxylate sulfatesand may contain other non-soap anionic surfactants or mixtures thereof.

Generally speaking, anionic surfactants useful herein are disclosed inU.S. Pat. No. 4,285,841, Barrat et al, issued Aug. 25, 1981, and in U.S.Pat. No. 3,919,678, Laughlin et al, issued Dec. 30, 1975, bothincorporated herein by reference.

Useful anionic surfactants include the water-soluble salts, particularlythe alkali metal, ammonium and alkylolammonium (e.g.,monoethanolammonium or triethanolammonium) salts, of organic sulfuricreaction products having in their molecular structure an alkyl groupcontaining from about 10 to about 20 carbon atoms and a sulfonic acid orsulfuric acid ester group. (Included in the term “alkyl” is the alkylportion of aryl groups.) Examples of this group of synthetic surfactantsare the alkyl sulfates, especially those obtained by sulfating thehigher alcohols (C₈-C₁₈ carbon atoms) such as those produced by reducingthe glycerides of tallow or coconut oil. Especially valuable are linearstraight chain alkylbenzene sulfonates in which the average number ofcarbon atoms in the alkyl group is from about 11 to 13, abbreviated asC₁₁-C₁₃LAS.

Other anionic surfactants herein are the water-soluble salts of alkylphenol ethylene oxide ether sulfates containing from about 1 to about 4units of ethylene oxide per molecule and from about 8 to about 12 carbonatoms in the alkyl group.

Other useful anionic surfactants herein include the water-soluble saltsof esters of α-sulfonated fatty acids containing from about 6 to 20carbon atoms in the fatty acid group and from about 1 to 10 carbon atomsin the ester group; water-soluble salts of 2-acyloxy-alkane-1-sulfonicacids containing from about 2 to 9 carbon atoms in the acyl group andfrom about 9 to about 23 carbon atoms in the alkane moiety;water-soluble salts of olefin sulfonates containing from about 12 to 24carbon atoms; and β-alkyloxy alkane sulfonates containing from about 1to 3 carbon atoms in the alkyl group and from about 8 to 20 carbon atomsin the alkane moiety.

The alkyl polyethoxylate sulfates usefule herein are of the formula

RO(C₂H₄O)_(x)SO₃ ⁻M⁺

wherein R is an alkyl chain having from about 10 to about 22 carbonatoms, saturated or unsaturated, M is a cation which makes the compoundwater-soluble, especially an alkali metal, ammonium or substitutedammonium cation, and x averages from about 0.5 to about 15.

Preferred alkyl sulfate surfactants are the non-ethoxylated C₁₂₋₁₅primary and secondary alkyl sulfates. Under cold water washingconditions, i.e., less than abut 65° F. (18.3° C.), it is preferred thatthere be a mixture of such ethoxylated and non-ethoxylated alkylsulfates.

Fatty Acids

Moreover, the anionic surfactant component herein comprises fatty acids.These include saturated and/or unsaturated fatty acids obtained fromnatural sources or synthetically prepared. Examples of fatty acidsinclude capric, lauric, myristic, palmitic, stearic, arachidic, andbehenic acid. Other fatty acids include palmitoleic, oleic, linoleic,linolenic, and ricinoleic acid.

Nonionic Detergent Surfactants

Suitable nonionic detergent surfactants are generally disclosed in U.S.Pat. No. 3,929,678, Laughlin et al., issued Dec. 30, 1975, and U.S. Pat.No. 4,285,841, Barrat et al, issued Aug. 25, 1981. Exemplary,non-limiting classes of useful nonionic surfactants include: C₈-C₁₈alkyl ethoxylates (“AE”), with EO about 1-22, including the so-callednarrow peaked alkyl ethoxylates and C₆-C₁₂ alkyl phenol alkoxylates(especially ethoxylates and mixed ethoxy/propoxy), alkyl dialkyl amineoxide, alkanoyl glucose amide, and mixtures thereof.

If nonionic surfactants are used, the compositions of the presentinvention will preferably contain up to about 10%, preferably from 0% toabout 5%, more preferably from 0% to about 3%, by weight of an nonionicsurfactant. Preferred are the ethoxylated alcohols and ethoxylated alkylphenols of the formula R(OC₂H₄)_(n)OH, wherein R is selected from thegroup consisting of aliphatic hydrocarbon radicals containing from about8 to about 15 carbon atoms and alkyl phenyl radicals in which the alkylgroups contain from about 8 to about 12 carbon atoms, and the averagevalue of n is from about 5 to about 15. These surfactants are more fullydescribed in U.S. Pat. No. 4,284,532, Leikhim et al, issued Aug. 18,1981. Particularly preferred are ethoxylated alcohols having an averageof from about 10 to abut 15 carbon atoms in the alcohol and an averagedegree of ethoxylation of from about 6 to about 12 moles of ethyleneoxide per mole of alcohol.

Other nonionic surfactants for use herein include:

The polyethylene, polypropylene, and polybutylene oxide condensates ofalkyl phenols. In general, the polyethylene oxide condensates arepreferred. These compounds include the condensation products of alkylphenols having an alkyl group containing from about 6 to about 12 carbonatoms in either a straight chain or branched chain configuration withthe alkylene oxide. In a preferred embodiment, the ethylene oxide ispresent in an amount equal to from about 5 to about 25 moles of ethyleneoxide per mole of alkyl phenol. Commercially available nonionicsurfactants of this type include Igepal® CO-630, marketed by the GAFCorporation; and Triton® X-45, X-114, X-100, and X-102, all marketed bythe Rohm & Haas Company. These compounds are commonly referred to asalkyl phenol alkoxylates, (e.g., alkyl phenol ethoxylates).

The condensation products of aliphatic alcohols with from about 1 toabout 25 moles of ethylene oxide. The alkyl chain of the aliphaticalcohol can either be straight or branched, primary or secondary, andgenerally contains from about 8 to about 22 carbon atoms. Particularlypreferred are the condensation products of alcohols having an alkylgroup containing from about 10 to about 20 carbon atoms with from about2 to about 18 moles of ethylene oxide per mole of alcohol. Examples ofcommercially available nonionic surfactants of this type includeTergitol® 15-S-9 (the condensation product of C₁₁-C₁₅ linear secondaryalcohol with 9 moles ethylene oxide), Tergitol® 24-L-6 NMW (thecondensation product of C₁₂-C₁₄ primary alcohol with 6 moles ethyleneoxide with a narrow molecular weight distribution), both marketed byUnion Carbide Corporation; Neodol® 45-9 (the condensation product ofC₁₄-C₁₅ linear alcohol with 9 moles of ethylene oxide), Neodol® 23-6.5(the condensation product of C₁₂-C₁₃ linear alcohol with 6.5 moles ofethylene oxide), Neodol® 45-7 (the condensation product of C₁₄-C₁₅linear alcohol with 7 moles of ethylene oxide), Neodol® 45-4 (thecondensation product of C₁₄-C₁₅ linear alcohol with 4 moles of ethyleneoxide), marketed by Shell Chemical Company, and Kyro® EOB (thecondensation product of C₁₃-C₁₅ alcohol with 9 moles ethylene oxide),marketed by The Procter & Gamble Company. Other commercially availablenonionic surfactants include Dobanol 91-8® marketed by Shell ChemicalCo. and Genapol UD-080® marketed by Hoechst. This category of nonionicsurfactant is referred to generally as “alkyl ethoxylates.”

The condensation products of ethylene oxide with a hydrophobic baseformed by the condensation of propylene oxide with propylene glycol. Thehydrophobic portion of these compounds preferably has a molecular weightof from about 1500 to about 1800 and exhibits water insolubility. Theaddition of polyoxyethylene moieties to this hydrophobic portion tendsto increase the water solubility of the molecule as a whole, and theliquid character of the product is retained up to the point where thepolyoxyethylene content is about 50% of the total weight of thecondensation product, which corresponds to condensation with up to about40 moles of ethylene oxide. Examples of compounds of this type includecertain of the commercially-available Pluronic® surfactants, marketed byBASF.

The condensation products of ethylene oxide with the product resultingfrom the reaction of propylene oxide and ethylenediamine. Thehydrophobic moiety of these products consists of the reaction product ofethylenediamine and excess propylene oxide, and generally has amolecular weight of from about 2500 to about 3000. This hydrophobicmoiety is condensed with ethylene oxide to the extent that thecondensation product contains from about 40% to about 80% by weight ofpolyoxyethylene and has a molecular weight of from about 5,000 to about11,000. Examples of this type of nonionic surfactant include certain ofthe commercially available Tetronic® compounds, marketed by BASF.

Semi-polar nonionic surfactants are a special category of nonionicsurfactants which include water-soluble amine oxides containing onealkyl moiety of from about 10 to about 18 carbon atoms and 2 moietiesselected from the group consisting of alkyl groups and hydroxyalkylgroups containing from about 1 to about 3 carbon atoms; water-solublephosphine oxides containing one alkyl moiety of from about 10 to about18 carbon atoms and 2 moieties selected from the group consisting ofalkyl groups and hydroxyalkyl groups containing from about 1 to about 3carbon atoms; and water-soluble sulfoxides containing one alkyl moietyof from about 10 to about 18 carbon atoms and a moiety selected from thegroup consisting of alkyl and hydroxyalkyl moieties of from about 1 toabout 3 carbon atoms.

Semi-polar nonionic detergent surfactants include the amine oxidesurfactants having the formula

wherein R³ is an alkyl, hydroxyalkyl, or alkyl phenyl group or mixturesthereof containing from about 8 to about 22 carbon atoms; R⁴ is analkylene or hydroxyalkylene group containing from about 2 to about 3carbon atoms or mixtures thereof; x is from 0 to about 3; and each R⁵ isan alkyl or hydroxyalkyl group containing from about 1 to about 3 carbonatoms or a polyethylene oxide group containing from about 1 to about 3ethylene oxide groups. The R⁵ groups can be attached to each other,e.g., through an oxygen or nitrogen atom, to form a ring structure.

These amine oxide surfactants in particular include C₁₀-C₁₈ alkyldimethyl amine oxides and C₈-C₁₂ alkoxy ethyl dihydroxy ethyl amineoxides.

Alkylpolysaccharides disclosed in U.S. Pat. No. 4,565,647, Llenado,issued Jan. 21, 1986, having a hydrophobic group containing from about 6to about 30 carbon atoms, preferably from about 10 to about 16 carbonatoms and a polysaccharide, e.g., a polyglycoside, hydrophilic groupcontaining from about 1.3 to about 10, preferably from about 1.3 toabout 3, most preferably from about 1.3 to about 2.7 saccharide units.Any reducing saccharide containing 5 or 6 carbon atoms can be used,e.g., glucose, galactose and galactosyl moieties can be substituted forthe glucosyl moieties. (Optionally the hydrophobic group is attached atthe 2-, 3-, 4-, etc. positions thus giving a glucose or galactose asopposed to a glucoside or galactoside.) The intersaccharide bonds canbe, e.g., between the one position of the additional saccharide unitsand the 2-, 3-, 4-, and/or 6-positions on the preceding saccharideunits.

Optionally, and less desirably, there can be a polyalkylene-oxide chainjoining the hydrophobic moiety and the polysaccharide moiety. Thepreferred alkyleneoxide is ethylene oxide. Typical hydrophobic groupsinclude alkyl groups, either saturated or unsaturated, branched orunbranched containing from about 8 to about 18, preferably from about 10to about 16, carbon atoms. Preferably, the alkyl group is a straightchain saturated alkyl group. The alkyl group can contain up to about 3hydroxy groups and/or the polyalkyleneoxide chain can contain up toabout 10, preferably less than 5, alkyleneoxide moieties. Suitable alkylpolysaccharides are octyl, nonyl, decyl, undecyldodecyl, tridecyl,tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl, di-, tri-,tetra-, penta-, and hexaglucosides, galactosides, lactosides, glucoses,fructosides, fructoses and/or galactoses. Suitable mixtures includecoconut alkyl, di-, tri-, tetra-, and pentaglucosides and tallow alkyltetra-, penta-, and hexa-glucosides.

The preferred alkylpolyglycosides have the formula

R²O(C_(n)H_(2n)O)_(t)(glycosyl)_(x)

wherein R² is selected from the group consisting of alkyl, alkyl-phenyl,hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which thealkyl groups contain from about 10 to about 18, preferably from about 12to about 14, carbon atoms; n is 2 or 3, preferably 2; t is from 0 toabout 10, preferably 0; and x is from about 1.3 to about 10, preferablyfrom about 1.3 to about 3, most preferably from about 1.3 to about 2.7.The glycosyl is preferably derived from glucose. To prepare thesecompounds, the alcohol or alkylpolyethoxy alcohol is formed first andthen reacted with glucose, or a source of glucose, to form the glucoside(attachment at the 1-position). The additional glycosyl units can thenbe attached between their 1-position and the preceding glycosyl units2-, 3-, 4- and/or 6-position, preferably predominantly the 2-position.

Fatty acid amide surfactants having the formula:

wherein R⁶ is an alkyl group containing from about 7 to about 21(preferably from about 9 to about 17) carbon atoms and each R⁷ isselected from the group consisting of hydrogen, C₁-C₄ alkyl, C₁-C₄hydroxyalkyl, and —(C²H₄O)_(x)H where x varies from about 1 to about 3.

Preferred amides are C₈-C₂₀ ammonia amides, monoethanolamides,diethanolamides, and isopropanolamides.

Cationic/amphoteric

Non-quaternary, cationic detersive surfactants can also be included indetergent compositions of the present invention. Cationic surfactantsuseful herein are described in U.S. Pat. No. 4,228,044, Cambre, issuedOct. 14, 1980.

Ampholytic surfactants can be incorporated into the detergentcompositions hereof. These surfactants can be broadly described asaliphatic derivatives of secondary or tertiary amines, or aliphaticderivatives of heterocyclic secondary and tertiary amines in which thealiphatic radical can be straight chain or branched. One of thealiphatic substituents contains at least about 8 carbon atoms, typicallyfrom about 8 to about 18 carbon atoms, and at least one contains ananionic water-solubilizing group, e.g., carboxy, sulfonate, sulfate. SeeU.S. Pat. No. 3,929,678 to Laughlin et al., issued Dec. 30, 1975 atcolumn 19, lines 18-35 for examples of ampholytic surfactants. Preferredamphoteric include C₁₂-C₁₈ alkyl ethoxylates (“AE”) including theso-called narrow peaked alkyl ethoxylates and C₆-C₁₂ alkyl phenolalkoxylates (especially ethoxylates and mixed ethoxy/propoxy), C₁₂-C₁₈betaines and sulfobetaines (“sultaines”), C₁₀-C₁₈ amine oxides, andmixtures thereof.

Polyhydroxy Fatty Acid Amide Surfactant

The detergent compositions hereof may also contain polyhydroxy fattyacid amide surfactant. The polyhydroxy fatty acid amide surfactantcomponent comprises compounds of the structural formula:

wherein: R¹ is H, C₁-C₄ hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl,or a mixture thereof, preferably C₁-C₄ alkyl, more preferably C₁ or C₂alkyl, most preferably C₁ alkyl (i.e., methyl); and R² is a C₅-C₃₁hydrocarbyl, preferably straight chain C₇-C₁₉ alkyl or alkenyl, morepreferably straight chain C₉-C₁₇ alkyl or alkenyl, most preferablystraight chain C₁₁-C₁₅ alkyl or alkenyl, or mixtures thereof; and Z is apolyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3hydroxyls directly connected to the chain, or an alkoxylated derivative(preferably ethoxylated or propoxylated) thereof. Z preferably will bederived from a reducing sugar in a reductive amination reaction; morepreferably Z will be a glycityl. Suitable reducing sugars includeglucose, fructose, maltose, lactose, galactose, mannose, and xylose. Asraw materials, high dextrose corn syrup, high fructose corn syrup, andhigh maltose corn syrup can be utilized as well as the individual sugarslisted above. These corn syrups may yield a mix of sugar components forZ. It should be understood that it is by no means intended to excludeother suitable raw materials. Z preferably will be selected from thegroup consisting of —CH₂—(CHOH)_(n)—CH₂OH, —CH(C₂OH)—(CHOH)_(n-1)—CH₂OH,—CH₂—(CHOH)₂(CHOR′)(CHOH)—CH₂OH, and alkoxylated derivatives thereof,where n is an integer from 3 to 5, inclusive, and R′ is H or a cyclic oraliphatic monosaccharide. Most preferred are glycityls wherein n is 4,particularly —CH₂—(CHOH)₄—CH₂OH.

R′ can be, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl,N-butyl, N-2-hydroxy ethyl, or N-2-hydroxy propyl.

R²—CO—N<can be, for example, cocamide, stearamide, oleamide, lauramide,myristamide, capricamide, palmitamide, tallowamide, etc.

Z can be 1-deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityl,1-deoxylactityl, 1-deoxygalactityl, 1-deoxymannityl,1-deoxymaltotriotityl, etc.

Methods for making polyhydroxy fatty acid amides are known in the art.In general, they can be made by reacting an alkyl amine with a reducingsugar in a reductive amination reaction to form a corresponding N-alkylpolyhydroxyamine, and then reacting the N-alkyl polyhydroxyamine with afatty aliphatic ester or triglyceride in a condensation/amidation stepto form the N-alkyl, N-polyhydroxy fatty acid amide product. Processesfor making compositions containing polyhydroxy fatty acid amides aredisclosed, for example, in G.B. Patent Specification 809,060, publishedFeb. 18, 1959, by Thomas Hedley & Co., Ltd., U.S. Pat. No. 2,965,576,issued Dec. 20, 1960 to E. R. Wilson, and U.S. Pat. No. 2,703,798,Anthony M. Schwartz, issued Mar. 8, 1955, and U.S. Pat. No. 1,985,424,issued Dec. 25, 1934 to Piggott, each of which is incorporated herein byreference.

Enzyme Stabiliziny System

Enzyme-containing, including but not limited to, liquid compositions,herein may comprise from about 0.001% to about 10%, preferably fromabout 0.005% to about 8%, most preferably from about 0.01% to about 6%,by weight of an enzyme stabilizing system. Such stabilizing systems can,for example, comprise calcium ion, boric acid, propylene glycol, shortchain carboxylic acids, boronic acids, and mixtures thereof, and aredesigned to address different stabilization problems depending on thetype and physical form of the detergent composition. See Severson, U.S.pat. No. 4,537,706 for a review of Borate stabilizers.

Suitable chlorine scavenger anions are widely known and readilyavailable, and, if used, can be salts containing ammonium cations withsulfite, bisulfite, thiosulfite, thiosulfate, iodide, etc. Antioxidantssuch as carbamate, ascorbate, etc., organic amines such asethylenediaminetetracetic acid (EDTA) or alkali metal salt thereof,monoethanolamine (MEA), and mixtures thereof can likewise be used. Otherconventional scavengers such as bisulfate, nitrate, chloride, sources ofhydrogen peroxide such as sodium perborate tetrahydrate, sodiumperborate monohydrate and sodium percarbonate, as well as phosphate,condensed phosphate, acetate, benzoate, citrate, formate, lactate,malate, tartrate, salicylate, etc., and mixtures thereof can be used ifdesired.

Enzymes

Suitable enzymes include proteases, amylases, lipases, cellulases,peroxidases, and mixtures thereof of any suitable origin, such asvegetable, animal, bacterial, fungal and yeast origin. Preferredselections are influenced by factors such as pH-activity and/orstability optima, thermostability, and stability to active bleach,detergents, builders and the like. In this respect bacterial or fungalenzymes are preferred, such as bacterial amylases and proteases, andfungal cellulases.

Enzymes are normally incorporated into detergent or detergent additivecompositions at levels sufficient to provide a “cleaning-effectiveamount”. The term “cleaning effective amount” refers to any amountcapable of producing a cleaning, stain removal, soil removal, whitening,deodorizing, or freshness improving effect on substrates such asdishware and the like. In practical terms for current commercialpreparations, the compositions herein may comprise from 0.001% to 5%,preferably 0.01%-1% by weight of a commercial enzyme preparation.Protease enzymes are usually present in such commercial preparations atlevels sufficient to provide from 0.005 to 0.1 Anson units (AU) ofactivity per gram of composition.

Other Enzymes

enzymes can be included in the present detergent compositions for avariety of purposes, including removal of protein-based,carbohydrate-based, or triglyceride-based stains from surfaces such astextiles or dishes, for the prevention of refugee dye transfer, forexample in laundering, and for fabric restoration. Suitable otherenzymes include proteases, lipases, peroxidases, and mixtures thereof ofany suitable origin, such as vegetable, animal, bacterial, fungal andyeast origin. Preferred selections are influenced by factors such aspH-activity and/or stability optima, thermostability, and stability toactive detergents, builders and the like. In this respect bacterial orfungal enzymes are preferred, such as bacterial amylases and proteases.

“Detersive enzyme”, as used herein, means any enzyme having a cleaning,stain removing or otherwise beneficial effect in a laundry, hard surfacecleaning or personal care detergent composition.

Enzymes are normally incorporated into detergent or detergent additivecompositions at levels sufficient to provide a “cleaning-effectiveamount”. The term “cleaning effective amount” refers to any amountcapable of producing a cleaning, stain removal, soil removal, whitening,deodorizing, or freshness improving effect on substrates such asfabrics, dishware and the like. In practical terms for currentcommercial preparations, typical amounts are up to about 5 mg by weight,more typically 0.01 mg to 3 mg, of active enzyme per gram of thedetergent composition. Stated otherwise, the compositions herein willtypically comprise from 0.001% to 5%, preferably 0.01%-1% by weight of acommercial enzyme preparation. Protease enzymes are usually present insuch commercial preparations at levels sufficient to provide from 0.005to 0.1 Anson units (AU) of activity per gram of composition. Higheractive levels may be desirable in highly concentrated detergentformulations.

Peroxidase enzymes may be used in combination with oxygen sources, e.g.,percarbonate, perborate, hydrogen peroxide, etc., for “solutionbleaching” or prevention of transfer of dyes or pigments removed fromsubstrates during the wash to other substrates present in the washsolution. Known peroxidases include horseradish peroxidase, ligninase,and haloperoxidases such as chloro- or bromo-peroxidase.Peroxidase-containing detergent compositions are disclosed in WO89099813 A, Oct. 19, 1989 to Novo and WO 8909813 A to Novo.

A range of enzyme materials and means for their incorporation intosynthetic detergent compositions is also disclosed in WO 9307263 A andWO 9307260 A to Genencor International, WO 8908694 A to Novo, and U.S.Pat. No. 3,553,139, Jan. 5, 1971 to McCarty et al. Enzymes are furtherdisclosed in U.S. Pat. No. 4,101,457, Place et al, Jul. 18, 1978, and inU.S. Pat. No. 4,507,219, Hughes, Mar. 26, 1985. Enzyme materials usefulfor liquid detergent formulations, and their incorporation into suchformulations, are disclosed in U.S. Pat. No. 4,261,868, Hora et al, Apr.14, 1981. Enzymes for use in detergents can be stabilized by varioustechniques. Enzyme stabilization techniques are disclosed andexemplified in U.S. Pat. No. 3,600,319, Aug. 17, 1971, Gedge et al, EP199,405 and EP 200,586, Oct. 29, 1986, Venegas. Enzyme stabilizationsystems are also described, for example, in U.S. Pat. No. 3,519,570. Auseful Bacillus, sp. AC13 giving proteases, xylanases and cellulases, isdescribed in WO 9401532 A to Novo.

Amylase

Amylase enzymes include those described in WO95/26397 and in co-pendingapplication by Novo Nordisk PCT/DK96/00056. These enzymes areincorporated into detergent compositions at a level from 0.00018% to0.060% pure enzyme by weight of the total composition, more preferablyfrom 0.00024% to 0.048% pure enzyme by weight of total weightcomposition.

Specific amylase enzymes for use in the detergent compositions of thepresent invention therefore include:

(a) α-amylases characterised by having a specific activity at least 25%higher than the specific activity of Termamyl® at a temperature range of25° C. to 55° C. and at a pH value in the range of 8 to 10, measured bythe Phadebas® α-amylase activity assay. Such Phadebas® α-amylaseactivity assay is described at pages 9-10, WO95/26397.

(b) α-amylases according (a) comprising the amino sequence shown in theSEQ ID listings in the above cited reference. or an α-amylase being atleast 80% homologous with the amino acid sequence shown in the SEQ IDlisting.

(c) α-amylases according (a) comprising the following amino sequence inthe N-terminal:His-His-Asn-Gly-Thr-Asn-Gly-Thr-Met-Met-Gln-Tyr-Phe-Glu-Trp-Tyr-Leu-Pro-Asn-Asp.

A polypeptide is considered to be X % homologous to the parent amylaseif a comparison of the respective amino acid sequences, performed viaalgorithms, such as the one described by Lipman and Pearson in Science227, 1985, p. 1435, reveals an identity of X %

(d) α-amylases according (a-c) wherein the α-amylase is obtainable froman alkalophilic Bacillus species; and in particular, from any of thestrains NCIB 12289, NCIB 12512, NCIB 12513 and DSM 935.

In the context of the present invention, the term “obtainable from” isintended not only to indicate an amylase produced by a Bacillus strainbyt also an amylase encoded by a DNA sequence isolated from such aBacillus strain and produced in an host organism transformed with saidDNA sequence.

(e) α-amylase showing positive immunological cross-reactivity withantibodies raised against an α-amylase having an amino acid sequencecorresponding respectively to those α-amylases in (a-d).

(f) Variants of the following parent α-amylases which (i) have one ofthe amino acid sequences shown in corresponding respectively to thoseα-amylases in (a-e), or (ii) displays at least 80% homology with one ormore of said amino acid sequences, and/or displays immunologicalcross-reactivity with an antibody raised against an α-amylase having oneof said amino acid sequences, and/or is encoded by a DNA sequence wichhybridizes with the same probe as a DNA sequence encoding an α-amylasehaving one of said amino acid sequence; in which variants:

1. at least one amino acid residue of said parent α-amylase has beendeleted; and/or

2. at least one amino acid residue of said parent α-amylase has beenreplaced by a different amino acid residue; and/or

3. at least one amino acid residue has been inserted relative to saidparent α-amylase; said variant having an α-amylase activity andexhibiting at least one of the following properties relative to saidparent α-amylase: increased thermostability, increased stability towardsoxidation, reduced Ca ion dependency, increased stability and/orα-amylolytic activity at neutral to relatively high pH values, increasedα-amylolytic activity at relatively high temperature and increase ordecrease of the isoelectric point-(pI) so as to better match the pIvalue for α-amylase variant to the pH of the medium.

The preferred amylayses of this invention are those described by thefollowing:

(a) α-amylases characterised by having a specific activity at least 25%higher than the specific activity of Termamyl® at a temperature range of25° C to 55° C. and at a pH value in the range of 8 to 10, measured bythe Phadebas® α-amylase activity assay;

(b) α-amylase showing positive immunological cross-reactivity withantibodies raised against an α-amylase having an amino acid sequencecorresponding respectively to those α-amylases in (a); and

(c) mixtures thereof.

Said variants are described in the patent application PCT/DK96/00056.

Other amylases suitable herein include, for example, α-amylasesdescribed in GB 1,296,839 to Novo; RAPIDASE®, InternationalBio-Synthetics, Inc. and TERMAMYL®, Novo. FUNGAMYL® from Novo isespecially useful.

Engineering of enzymes for improved stability, e.g., oxidativestability, is known. See, for example J. Biological Chem., Vol. 260, No.11, Jun. 1985, pp. 6518-6521. Certain preferred embodiments of thepresent compositions can make use of amylases having improved stabilityin detergents, especially improved oxidative stability as measuredagainst a reference-point of TERMAMYL® in commercial use in 1993. Thesepreferred amylases herein share the characteristic of being“stability-enhanced” amylases, characterized, at a minimum, by ameasurable improvement in one or more of: oxidative stability, e.g., tohydrogen peroxide/tetraacetylethylenediamine in buffered solution at pH9-10; thermal stability, e.g., at common wash temperatures such as about60° C.; or alkaline stability, e.g., at a pH from about 8 to about 11,measured versus the above-identified reference-point amylase. Stabilitycan be measured using any of the art-disclosed technical tests. See, forexample, references disclosed in WO 9402597.

Stability-enhanced amylases can be obtained from Novo or from GenencorInternational. One class of highly preferred amylases herein have thecommonality of being derived using site-directed mutagenesis from one ormore of the Bacillus amylases, especially the Bacillus α-amylases,regardless of whether one, two or multiple amylase strains are theimmediate precursors. Such preferred amylases include (a) an amylaseaccording to the hereinbefore incorporated WO 9402597, Novo, Feb. 3,1994, as further illustrated by a mutant in which substitution is made,using alanine or threonine, preferably threonine, of the methionineresidue located in position 197 of the B. licheniformis alpha-amylase,known as TERMAMYL®, or the homologous position variation of a similarparent amylase, such as B. amyloliquefaciens, B. subtilis, or B.stearothermophilus; (b) stability-enhanced amylases as described byGenencor International in a paper entitled “Oxidatively Resistantalpha-Amylases” presented at the 207th American Chemical SocietyNational Meeting, Mar. 13-17 1994, by C. Mitchinson. Therein it wasnoted that bleaches in detergents inactivate alpha-amylases but thatimproved oxidative stability amylases have been made by Genencor from B.licheniformis NCIB8061. Methionine (Met) was identified as the mostlikely residue to be modified. Met was substituted, one at a time, inpositions 8, 15, 197, 256, 304, 366 and 438 leading to specific mutants,particularly important being M197L and M197T with the M197T variantbeing the most stable expressed variant. Stability was measured inCASCADE® and SUNLIGHT®; (c) particularly preferred amylases hereininclude amylase variants having additional modification in the immediateparent as described in WO 9510603 A and are available from the assignee,Novo, as DURAMYL®. Other particularly preferred oxidative stabilityenhanced amylase include those described in WO 9418314 to GenencorInternational and WO 9402597 to Novo. Any other oxidativestability-enhanced amylase can be used, for example as derived bysite-directed mutagenesis from known chimeric, hybrid or simple mutantparent forms of available amylases. Other preferred enzyme modificationsare accessible. See WO 9509909 A to Novo.

Proteases

Suitable examples of proteases are the subtilisins which are obtainedfrom particular strains of B. subtilis and B. licheniformis. Onesuitable protease is obtained from a strain of Bacillus, having maximumactivity throughout the pH range of 8-12, developed and sold asESPERASE® by Novo Industries A/S of Denmark, hereinafter “Novo”. Thepreparation of this enzyme and analogous enzymes is described in GB1,243,784 to Novo. Other suitable proteases include ALCALASE® andSAVINASE® from Novo and MAXATASE® from International Bio-Synthetics,Inc., The Netherlands; as well as Protease A as disclosed in EP 130,756A, Jan. 9, 1985 and Protease B as disclosed in EP 303,761 A, Apr. 28,1987 and EP 130,756 A, Jan. 9, 1985. See also a high pH protease fromBacillus sp. NCIMB 40338 described in WO 9318140 A to Novo. Enzymaticdetergents comprising protease, one or more other enzymes, and areversible protease inhibitor are described in WO 9203529 A to Novo.Other preferred proteases include those of WO 9510591 A to Procter &Gamble. When desired, a protease having decreased adsorption andincreased hydrolysis is available as described in WO 9507791 to Procter& Gamble. A recombinant trypsin-like protease for detergents suitableherein is described in WO 9425583 to Novo.

In more detail, an especially preferred protease, referred to as“Protease D” is a carbonyl hydrolase variant having an amino acidsequence not found in nature, which is derived from a precursor carbonylhydrolase by substituting a different amino acid for a plurality ofamino acid residues at a position in said carbonyl hydrolase equivalentto position +76, preferably also in combination with one or more aminoacid residue positions equivalent to those selected from the groupconsisting of +99, +101, +103, +104, +107, +123, +27, +105, +109, +126,+128, +135, +156, +166, +195, +197, +204, +206, +210, +216, +217, +218,+222, +260, +265, and/or +274 according to the numbering of Bacillusamyloliquefaciens subtilisin, as described in the patent applications ofA. Baeck, et al, entitled “Protease-Containing Cleaning Compositions”having U.S. Ser. No. 08/322,676, and C. Ghosh, et al, “BleachingCompositions Comprising Protease Enzymes” having U.S. Ser. No.08/322,677, both filed Oct. 13, 1994.

Preferred proteolytic enzymes are also modified bacterial serineproteases, such as those described in European Patent Application SerialNumber 87 303,761.8, filed Apr. 28, 1987 (particularly pages 17, 24 and98), and which is called herein “Protease B”, and in European PatentApplication 199,404, Venegas, published Oct. 29, 1986, which refers to amodified bacterial serine proteolytic enzyme which is called “ProteaseA” herein, Protease A as disclosed in EP 130,756 A, Jan. 9, 1985 andProtease B as disclosed in EP 303,761 A, Apr. 28, 1987 and EP 130,756 A,Jan. 9, 1985.

Also preferred proteases are subtilisin enzymes, in particular BPN′,that have been modified by mutating the various nucleotide sequencesthat code for the enzyme, thereby modifying the amino acid sequence ofthe enzyme. These modified subtilisin enzymes have decreased adsorptionto and increased hydrolysis of an insoluble substrate as compared to thewild-type subtilisin. Also suitable are mutant genes encoding for suchBPN′ variants.

Preferred BPN′ variants comprise wild-type amino acid sequence whereinthe wild-type amino acid sequence at one or more of positions 199, 200,201, 202, 203, 204, 205, 206, 207, 208, 209, 210, 211, 212, 213, 214,215, 216, 218, 219 or 220 is substituted; wherein the BPN′ variant hasdecreased adsorption to, and increased hydrolysis of, an insolublesubstrate as compared to the wild-type subtilisin BPN′. Preferably, thepositions having a substituted amino acid are 199, 200, 201, 202, 205,207, 208, 209, 210, 211, 212, or 215; more preferably, 200, 201, 202,205 or 207.

Preferred protease enzymes for use according to the present inventionalso include the subtilisin 309 variants. These protease enzymes includeseveral classes of subtilisin 309 variants.

A. Loon Region 6 Substitution Variants

These subtilisin 309 variants have a modified amino acid sequence ofsubtilisin 309 wild-type amino acid sequence, wherein the modified aminoacid sequence comprises a substitution at one or more of positions 193,194, 195, 196, 197, 199, 200, 201, 202, 203, 204, 205, 206, 207, 208,209, 210, 211, 212, 213 or 214; whereby the subtilisin 309 variant hasdecreased adsorption to, and increased hydrolysis of, an insolublesubstrate as compared to the wild-type subtilisin 309. Preferably theseproteases have amino acids substituted at 193, 194, 195, 196, 199, 201,202, 203, 204, 205, 206 or 209; more preferably 194, 195, 196, 199 or200.

B. Multi-Loop Regions Substitution Variants

These subtilisin 309 variants may also be a modified amino acid sequenceof subtilisin 309 wild-type amino acid sequence, wherein the modifiedamino acid sequence comprises a substitution at one or more positions inone or more of the first, second, third, fourth, or fifth loop regions;whereby the subtilisin 309 variant has decreased adsorption to, andincreased hydrolysis of, an insoluble substrate as compared to thewild-type subtilisin 309.

C. Substitutions at Positions Other Than the Loop Regions

In addition, one or more substitution of wild-type subtilisin 309 may bemade at positions other than positions in the loop regions, for example,at position 74. If the additional substitution to the subtilisin 309 ismad at position 74 alone, the substitution is preferably with Asn, Asp,Glu, Gly, His, Lys, Phe or Pro, preferably His or Asp. Howevermodifications can be made to one or more loop positions as well asposition 74, for example residues 97, 99, 101, 102, 105 and 121.

Subtilisin BPN′ variants and subtilisin 309 variants are furtherdescribed in WO 95/29979, WO 95/30010 and WO 95/30011, all of which werepublished Nov. 9, 1995, all of which are incorporated herein byreference.

Lipases

Suitable lipase enzymes for detergent usage include those produced bymicroorganisms of the Pseudomonas group, such as Pseudomonas stutzeriATCC 19.154, as disclosed in GB 1,372,034. See also lipases in JapanesePatent Application 53,20487, laid open Feb. 24, 1978. Other suitablelipases include those which show a positive immunological cross-reactionwith the antibody of the lipase, produced by the microorganismPseudomonas fluorescens IAM 1057. This lipase is available from AmanoPharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P“Amano,” hereinafter referred to as “Amano-P”. Further suitable lipasesare lipases such as M1 Lipase^(R) and Lipomax^(R) (Gist-Brocades). Othersuitable commercial lipases include Amano-CES, lipases ex Chromobacterviscosum, e.g. Chromobacter viscosum var. lipolyticum NRRLB 3673 fromToyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipases from U.S.Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and lipasesex Pseudomonas gladioli. LIPOLASE® enzyme derived from Humicolalanuginosa and commercially available from Novo, see also EP 341,947, isa preferred lipase for use herein. Lipase variants stabilized againstperoxidase enzymes are described in WO 9414951 A to Novo. See also WO9205249 and RD 94359044.

Highly preferred lipases are the D96L lipolytic enzyme variant of thenative lipase derived from Humicola lanuginosa as described in U.S. Ser.No. 08/341,826. (See also patent application WO 92/05249 viz. whereinthe native lipase ex Humicola lanuginosa aspartic acid (D) residue atposition 96 is changed to Leucine (L). According to this nomenclaturesaid substitution of aspartic acid to Leucine in position 96 is shownas: D96L.) Preferably the Humicola lanuginosa strain DSM 4106 is used.

In spite of the large number of publications on lipase enzymes, only thelipase derived from Humicola lanuginosa and produced in Aspergillusoryzae as host has so far found widespread application as additive forfabric washing products. It is available from Novo Nordisk under thetradename Lipolase™, as noted above. In order to optimize the stainremoval performance of Lipolase, Novo Nordisk have made a number ofvariants. As described in WO 92/05249, the D96L variant of the nativeHumicola lanuginosa lipase improves the lard stain removal efficiency bya factor 4.4 over the wild-type lipase (enzymes compared in an amountranging from 0.075 to 2.5 mg protein per liter). Research Disclosure No.35944 published on Mar. 10, 1994, by Novo Nordisk discloses that thelipase variant (D96L) may be added in an amount corresponding to0.001-100-mg (5-500,000 LU/liter) lipase variant per liter of washliquor.

Lipase enzyme is incorporated into the composition in accordance withthe invention at a level of from 50 LU to 8500 LU per liter washsolution. Preferably the variant D96L is present at a level of from 100LU to 7500 LU per liter of wash solution. More preferably at a level offrom 150 LU to 5000 LU per liter of wash solution.

The lipases and/or cutinases are normally incorporated in the detergentcomposition at levels from 0.0001% to 2% of active enzyme by weight ofthe detergent composition.

Also suitable are cutinases [EC 3.1.1.50] which can be considered as aspecial kind of lipase, namely lipases which do not require interfacialactivation. Addition of cutinases to detergent compositions have beendescribed in e.g. WO-A-88/09367 (Genencor).

Cellulase Enzymes

The laundry detergent compositions according to the present inventionmay further comprise at least 0.001% by weight, preferably at leastabout 0.01%, of a cellulase enzyme. However, an effective amount ofcellulase enzyme is sufficient for use in the laundry detergentcompositions described herein. The term “an effective amount” refers toany amount capable of producing a cleaning, stain removal, soil removal,whitening, deodorizing, or freshness improving effect on substrates suchas fabrics, dishware and the like. The compositions herein willtypically comprise from about 0.05% to about 2%, preferably from about0.1% to about 1.5% by weight of a commercial enzyme preparation. Thecellulase enzymes of the present invention are usually present in suchcommercial preparations at levels sufficient to provide from 0.005 to0.1 Anson units (AU) of activity per gram of composition. Preferably,the optimum pH of the enzyme-containing composition is between about 7and about 9.5.

U.S. Pat. No. 4,435,307, Barbesgaard et al, issued Mar. 6, 1984,discloses cellulase produced from Humicola insolens. Examples of othersuitable cellulases include those produced by a strain of Humicolainsolens, Humicola grisea var. thermoidea, and cellulases produced by aspecies of Bacillus sp. or Aeromonas sp. Other useful cellulases arethose extracted from the hepatopancreas of the marine mollusc DolabellaAuricula Solander. Suitable cellulases are also disclosed in thefollowing: GB 2,075,028 A (Novo Industri A/S); GB 2,095,275 A (Kao SoapCo., Ltd.); and Horikoshi et al, U.S. Pat. No. 3,844,890 (RikagakuKenkyusho). In addition, suitable cellulases and methods for theirpreparation are described in PCT International Publication Number WO91/17243, published Nov. 14, 1991, by Novo Nordisk A/S.

Cellulases are known in the art and can be obtained from suppliers underthe tradenames: Celluzyme®, Endolase®, and Carezyme®.

For industrial production of the cellulases herein it is preferred thatrecombinant DNA techniques be employed. However other techniquesinvolving adjustments of fermentations or mutation of the microorganismsinvolved can be employed to ensure overproduction of the desiredenzymatic activities. Such methods and techniques are known in the artand may readily be carried out by persons skilled in the art.

Perfumes

Perfumes and perfumery ingredients useful in the present compositionsand processes comprise a wide variety of natural and synthetic chemicalingredients, including, but not limited to, aldehydes, ketones, esters,and the like. Also included are various natural extracts and essenceswhich can comprise complex mixtures of ingredients, such as orange oil,lemon oil, rose extract, lavender, musk, patchouli, balsamic essence,sandalwood oil, pine oil, cedar, and the like. Finished perfumes cancomprise extremely complex mixtures of such ingredients. Finishedperfumes typically comprise from about 0.01% to about 4%, by weight, ofthe detergent compositions herein, and individual perfumery ingredientscan comprise from about 0.0001% to about 90% of a finished perfumecomposition.

Material Care Agents

The present compositions may optionally contain as corrosion inhibitorsand/or anti-tarnish aids one or more material care agents such assilicates. Material care agents include bismuth salts, transition metalsalts such as those of manganese, certain types of paraffin, triazoles,pyrazoles, thiols, mercaptans, aluminium fatty acid salts, and mixturesthereof and are preferably incorporated at low levels, e.g., from about0.01% to about 5% of the composition. A preferred paraffin oil is apredominantly branched aliphatic hydrocarbon comprising from about 20 toabout 50 carbon atoms with a ratio of cyclic to noncyclic hydrocarbonsof about 32 to 68 sold by Wintershall, Salzbergen, Germany as WINOG 70®.Bi(NO₃)₃ may be added. Other corrosion inhibitors are illustrated bybenzotriazole, thiols including thionaphtol and thioanthranol, andfinely divided aluminium fatty acid salts. All such materials willgenerally be used judiciously so as to avoid producing spots or films onglassware or compromising the bleaching action of the compositions. Forthis reason, it may be preferred to formulate without mercaptananti-tarnishes which are quite strongly bleach-reactive or common fattycarboxylic acids which precipitate with calcium.

Chelating Agents

The detergent compositions herein may also optionally contain one ormore iron and/or manganese chelating agents. Such chelating agents canbe selected from the group consisting of amino carboxylates, aminophosphonates, polyfunctionally-substituted aromatic chelating agents andmixtures therein, all as hereinafter defined. Without intending to bebound by theory, it is believed that the benefit of these materials isdue in part to their exceptional ability to remove iron and manganeseions from washing solutions by formation of soluble chelates.

Amino carboxylates useful as optional chelating agents includeethylenediaminetetracetates, N-hydroxyethylethylenediaminetriacetates,nitrilotriacetates, ethylenediamine tetraproprionates,triethylenetetraaminehexacetates, diethylenetriaminepentaacetates, andethanoldiglycines, alkali metal, ammonium, and substituted ammoniumsalts therein and mixtures therein.

Amino phosphonates are also suitable for use as chelating agents in thecompositions of the invention when at lease low levels of totalphosphorus are permitted in detergent compositions, and includeethylenediaminetetrakis (methylenephosphonates) as DEQUEST. Preferred,these amino phosphonates to not contain alkyl or alkenyl groups withmore than about 6 carbon atoms.

Polyfunctionally-substituted aromatic chelating agents are also usefulin the compositions herein. See U.S. Pat. No. 3,812,044, issued May 21,1974, to Connor et al. Preferred compounds of this type in acid form aredihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene.

A preferred biodegradable chelator for use herein is ethylenediaminedisuccinate (“EDDS”), especially the [S,S] isomer as described in U.S.Pat. No. 4,704,233, Nov. 3, 1987, to Hartman and Perkins.

The compositions herein may also contain water-soluble methyl glycinediacetic acid (MGDA) salts (or acid form) as a chelant or co-builderuseful with, for example, insoluble builders such as zeolites, layeredsilicates and the like.

If utilized, these chelating agents will generally comprise from about0.1% to about 15% by weight of the detergent compositions herein. Morepreferably, if utilized, the chelating agents will comprise from about0.1% to about 3.0% by weight of such compositions.

Polymeric Dispersing Agents

Polymeric dispersing agents can advantageously be utilized at levelsfrom about 0.1% to about 7%, by weight, in the compositions herein,especially in the presence of zeolitc and/or layered silicate builders.Suitable polymeric dispersing agents include polymeric polycarboxylatesand polyethylene glycols, although others known in the art can also beused. It is believed, though it is not intended to be limited by theory,that polymeric dispersing agents enhance overall detergent builderperformance, when used in combination with other builders (includinglower molecular weight polycarboxylates) by crystal growth inhibition,particulate soil release peptization, and anti-redeposition.

Polymeric polycarboxylate materials can be prepared by polymerizing orcopolymerizing suitable unsaturated monomers, preferably in their acidform. Unsaturated monomeric acids that can be polymerized to formsuitable polymeric polycarboxylates include acrylic acid, maleic acid(or maleic anhydride), fumaric acid, itaconic acid, aconitic acid,mesaconic acid, citraconic acid and methylenemalonic acid. The presencein the polymeric polycarboxylates herein or monomeric segments,containing no carboxylate radicals such as vinylmethyl ether, styrene,ethylene, etc. is suitable provided that such segments do not constitutemore than about 40% by weight.

Particularly suitable polymeric polycarboxylates can be derived fromacrylic acid. Such acrylic acid-based polymers which are useful hereinare the water-soluble salts of polymerized acrylic acid. The averagemolecular weight of such polymers in the acid form preferably rangesfrom about 2,000 to 10,000, more preferably from about 4,000 to 7,000and most preferably from about 4,000 to 5,000. Water-soluble salts ofsuch acrylic acid polymers can include, for example, the alkali metal,ammonium and substituted ammonium salts. Soluble polymers of this typeare known materials. Use of polyacrylates of this type in detergentcompositions has been disclosed, for example, in Diehl, U.S. Pat. No.3,308,067, issued Mar. 7, 1967.

Acrylic/maleic-based copolymers may also be used as a preferredcomponent of the dispersing/anti-redeposition agent. Such materialsinclude the water-soluble salts of copolymers of acrylic acid and maleicacid. The average molecular weight of such copolymers in the acid formpreferably ranges from about 2,000 to 100,000, more preferably fromabout 5,000 to 75,000, most preferably from about 7,000 to 65,000. Theratio of acrylate to maleate segments in such copolymers will generallyrange from about 30:1 to about 1:1, more preferably from about 10:1 to2:1. Water-soluble salts of such acrylic acid/maleic acid copolymers caninclude, for example, the alkali metal, ammonium and substitutedammonium salts. Soluble acrylate/maleate copolymers of this type areknown materials which are described in European Patent Application No.66915, published Dec. 15, 1982, as well as in EP 193,360, published Sep.3, 1986, which also describes such polymers comprisinghydroxypropylacrylate. Still other useful dispersing agents include themaleic/acrylic/vinyl alcohol terpolymers. Such materials are alsodisclosed in EP 193,360, including, for example, the 45/45/10 terpolymerof acrylic/maleic/vinyl alcohol.

Other polymeric materials which can be included are polypropylene glycol(PPG), propylene glycol (PG), and polyethylene glycol (PEG). PEG canexhibit dispersing agent performance as well as act as a clay soilremoval-antiredeposition agent. Typical molecular weight ranges forthese purposes range from about 500 to about 100,000, preferably fromabout 1,000 to about 50,000, more preferably from about 1,500 to about10,000.

Polyaspartate and polyglutamate dispersing agents may also be used,especially in conjunction with zeolite builders. Dispersing agents suchas polyaspartate preferably have a molecular weight (avg.) of about10,000.

Alkoxylated polycarboxylates such as those prepared from polyacrylatesare useful herein to provide additional grease removal performance. Suchmaterials are described in WO 91/08281 and PCT 90/01815 at p. 4 et seq.Chemically, these materials comprise polyacrylates having one ethoxyside-chain per every 7-8 acrylate units. The side-chains are of theformula —(CH₂CH₂O)_(m)(CH₂)_(n)CH₃ wherein m is 2-3 and n is 6-12. Theside-chains are ester-linked to the polyacrylate “backbone” to provide a“comb” polymer type structure. The molecular weight can vary, but istypically in the range of about 2000 to about 50,000. Such alkoxylatedpolycarboxylates can comprise from about 0.05% to about 10%, by weight,of the compositions herein.

The levels of these dispersants used can range from about 0.1% to about10%, typically from about 0.4% to about 5%, by weight. These dispersantscan be synthesized following the methods outline in U.S. Pat. No.4,664,848, or other ways known to those skilled in the art.

Dye Fixative Materials

optionally but preferred for use herein are selected dye fixativematerials which do not form precipitates with anionic surfactant.

The selected dye fixatives useful herein may be in the form ofunpolymerized materials, oligomers or polymers. Moreover, the preferreddye fixatives useful herein are cationic. The dye fixative component ofthe compositions herein will generally comprise from about 0.1% to 5% bythe weight of the composition. More preferably, such dye fixativematerials will comprise from about 0.5% to 4% by weight of thecompositions, most preferably from about 1% to 3%. Such concentrationsshould be sufficient to provide from about 10 to 100 ppm of the dyefixative in the aqueous washing solutions formed from the laundrydetergent compositions herein. More prefearably from about 20 to 60 ppmof the dye fixative will be delivered to the aqueous washing solution,most preferably about 50 ppm.

The non-precipitating dye fixatives useful herein include a number thatare commercially marketed by CLARLANT Corporation under the Sandofix®,Sandolec® and Polymer VRN® tradenames. These include, for example,Sandofix SWE®, Sandofix WA®, Sandolec CT®, Sandolec CS®, Sandolec C1®,Sandolec CF®, Sandolec WA® and Polymer VRN®. Other suitable dyefixatives are marketed by Ciba-Geigy Corporation under the tradenameCassofix FRN-300® and by Hoechst Celanese Corporation under thetradename Tinofix EW®.

Builders

Detergent builders can optionally but preferably be included in thecompositions herein, for example to assist in controlling mineral,especially Ca and/or Mg, hardness in wash water or to assist in theremoval of particulate soils from surfaces. Builder level can varywidely depending upon end use and physical form of the composition.Built detergents typically comprise at least about 1% builder. Liquidformulations typically comprise about 5% to about 50%, more typically 5%to 35% of builder. Lower or higher levels of builders are not excluded.For example, certain detergent additive or high-surfactant formulationscan be unbuilt.

Suitable builders herein can be selected from the group consisting ofphosphates and polyphosphates, especially the sodium salts; silicatesincluding water-soluble and hydrous solid types and including thosehaving chain-, layer-, or three-dimensional-structure as well asamorphous-solid or non-structured-liquid types; carbonates,bicarbonates, sesquicarbonates and carbonate minerals other than sodiumcarbonate or sesquicarbonate; aluminosilicates; organic mono-, di-,tri-, and tetracarboxylates especially water-soluble nonsurfactantcarboxylates in acid, sodium, potassium or alkanolammonium salt form, aswell as oligomeric or water-soluble low molecular weight polymercarboxylates including aliphatic and aromatic types; and phytic acid.These may be complemented by borates, e.g., for pH-buffering purposes,or by sulfates, especially sodium sulfate and any other fillers orcarriers which may be important to the engineering of stable surfactantand/or builder-containing detergent compositions.

Builder mixtures, sometimes termed “builder systems” can be used andtypically comprise two or more conventional builders, optionallycomplemented by chelants, pH-buffers or fillers, though these lattermaterials are generally accounted for separately when describingquantities of materials herein.

P-containing detergent builders often preferred where permitted bylegislation include, but are not limited to, the alkali metal, ammoniumand alkanolammonium salts of polyphosphates exemplified by thetripolyphosphates, pyrophosphates, glassy polymeric meta-phosphates; andphosphonates.

Suitable silicate builders include alkali metal silicates, particularlythose liquids and solids having a SiO₂:Na₂O ratio in the range 1.6:1 to3.2:1, including, particularly for automatic dishwashing purposes, solidhydrous 2-ratio silicates marketed by PQ Corp. under the tradenameBRITESIL®, e.g., BRITESIL H2O; and layered silicates, e.g., thosedescribed in U.S. pat. No. 4,664,839, May 12, 1987, H. P. Rieck. Seepreparative methods in German DE-A-3,417,649 and DE-A-3,742,043.

Also suitable for use herein are synthesized crystalline ion exchangematerials or hydrates thereof as taught in U.S. Pat. No. 5,427,711,Sakaguchi et al, Jun. 27, 1995.

Suitable carbonate builders include alkaline earth and alkali metalcarbonates as disclosed in German Patent Application No. 2,321,001published on Nov. 15, 1973.

Aluminosilicate builders are especially useful in granular detergents,but can also be incorporated in liquids. Suitable for the presentpurposes are those having empirical formula:[M_(z)(AlO₂)_(z)(SiO₂)_(v)].xH₂O wherein z and v are integers of atleast 6, the molar ratio of z to v is in the range from 1.0 to 0.5, andx is an integer from 15 to 264. Aluminosilicates can be crystalline oramorphous, naturally-occurring or synthetically derived. Analuminosilicate production method is in U.S. Pat. No. 3,985,669,Krummel, et al, Oct. 12, 1976. Preferred synthetic crystallinealuminosilicate ion exchange materials are available as Zeolite A,Zeolite P (B), Zeolite X and, to whatever extent this differs fromZeolite P, the so-called Zeolite MAP.

Suitable organic detergent builders include polycarboxylate compounds,including water-soluble nonsurfactant dicarboxylates andtricarboxylates. More typically builder polycarboxylates have aplurality of carboxylate groups, preferably at least 3 carboxylates.Carboxylate builders can be formulated in acid, partially neutral,neutral or overbased form. When in salt form, alkali metals, such assodium, potassium, and lithium, or alkanolammonium salts are preferred.Polycarboxylate builders include the ether polycarboxylates, such asoxydisuccinate, see Berg, U.S. Pat. No. 3,128,287, Apr. 7, 1964, andLamberti et al, U.S. Pat. No. 3,635,830, Jan. 18, 1972; “TMS/TDS”builders of U.S. Pat. No. 4,663,071, Bush et al, May 5, 1987; and otherether carboxylates including cyclic and alicyclic compounds, such asthose described in U.S. Pat. Nos. 3,923,679; 3,835,163; 4,158,635;4,120,874 and 4,102,903.

Other suitable builders are the ether hydroxypolycarboxylates,copolymers of maleic anhydride with ethylene or vinyl methyl ether;1,3,5-trihydroxy benzene-2,4,6-trisulphonic acid;carboxymethyloxysuccinic acid; the various alkali metal, ammonium andsubstituted ammonium salts of polyacetic acids such as ethylenediaminetetraacetic acid and nitrilotriacetic acid; as well as mellitic acid,succinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid,carboxymethyloxysuccinic acid, and soluble salts thereof.

Oxydisuccinates are also especially useful in such compositions andcombinations.

Certain detersive surfactants or their short-chain homologs also have abuilder action. For unambiguous formula accounting purposes, when theyhave surfactant capability, these materials are summed up as detersivesurfactants. Preferred types for builder functionality are illustratedby: 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related compoundsdisclosed in U.S. Pat. No. 4,566,984, Bush, Jan. 28, 1986. Succinic acidbuilders include the C₅-C₂₀ alkyl and alkenyl succinic acids and saltsthereof. Succinate builders also include: laurylsuccinate,myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred),2-pentadecenylsuccinate, and the like. Lauryl-succinates are describedin European Patent Application 86200690.5/0,200,263, published Nov. 5,1986. Fatty acids, e.g., C₁₂-C₁₈ monocarboxylic acids, can also beincorporated into the compositions as surfactant/builder materials aloneor in combination with the aforementioned builders, especially citrateand/or the succinate builders, to provide additional builder activity.Other suitable polycarboxylates are disclosed in U.S. Pat. No.4,144,226, Crutchfield et al, Mar. 13, 1979 and in U.S. Pat. No.3,308,067, Diehl, Mar. 7, 1967. See also Diehl, U.S. Pat. No. 3,723,322.

Other types of inorganic builder materials which can be used have theformula (M_(x))_(i) Ca_(y) (CO₃)_(z) wherein x and i are integers from 1to 15, y is an integer from 1 to 10, z is an integer from 2 to 25, M_(i)are cations, at least one of which is a water-soluble, and the equationΣ_(i=1-15)(x_(i) multiplied by the valence of M_(i))+2y=2z is satisfiedsuch that the formula has a neutral or “balanced” charge. These buildersare referred to herein as “Mineral Builders”.

Polymeric Soil Release Agent

Known polymeric soil release agents, hereinafter “SRA” or “SRA's”, canoptionally be employed in the present detergent compositions. Ifutilized, SRA's will generally comprise from 0.01% to 10.0%, typicallyfrom 0.1% to 5%, preferably from 0.2% to 3.0% by weight, of thecomposition.

SRA's can include a variety of charged, e.g., anionic or even cationic(see U.S. Pat. No. 4,956,447), as well as noncharged monomer units andstructures may be linear, branched or even star-shaped. They may includecapping moieties which are especially effective in controlling molecularweight or altering the physical or surface-active properties. Structuresand charge distributions may be tailored for application to differentfiber or textile types and for varied detergent or detergent additiveproducts.

Suitable SRA's include a sulfonated product of a substantially linearester oligomer comprised of an oligomeric ester backbone ofterephthaloyl and oxyalkyleneoxy repeat units, for example as describedin U.S. Pat. No. 4,968,451, Nov. 6, 1990 to J. J. Scheibel and E. P.Gosselink. See U.S. Pat. No. 4,711,730, Dec. 8, 1987 to Gosselink et al,for examples of those produced by transesterification/oligomerization ofpoly(ethyleneglycol) methyl ether, DMT, PG and poly(ethyleneglycol)(“PEG”). Partly- and fully-anionic-end-capped oligomeric esters of U.S.Pat. No. 4,721,580, Jan. 26, 1988 to Gosselink, such as oligomers fromethylene glycol (“EG”), PG, DMT andNa-3,6-dioxa-8-hydroxyoctanesulfonate; the nonionic-capped blockpolyester oligomeric compounds of U.S. Pat. No. 4,702,857, Oct. 27, 1987to Gosselink, for example produced from DMT, Me-capped PEG and EG and/orPG, or a combination of DMT, EG and/or PG, Me-capped PEG andNa-dimethyl-5-sulfoisophthalate; and the anionic, especially sulfoaroyl,end-capped terephthalate esters of U.S. Pat. No. 4,877,896, Oct. 31,1989 to Maldonado, Gosselink et al.

SRA's also include simple copolymeric blocks of ethylene terephthalateor propylene terephthalate with polyethylene oxide or polypropyleneoxide terephthalate, see U.S. Pat. No. 3,959,230 to Hays, May 25, 1976and U.S. Pat. No. 3,893,929 to Basadur, Jul. 8, 1975; cellulosicderivatives such as the hydroxyether cellulosic polymers available asMETHOCEL from Dow; and the C₁-C₄ alkylcelluloses and C₄ hydroxyalkylcelluloses; see U.S. Pat. No. 4,000,093, Dec. 28, 1976 to Nicol, et al.Suitable SRA's characterised by poly(vinyl ester) hydrophobe segmentsinclude graft copolymers of poly(vinyl ester), e.g., C₁-C₆ vinyl esters,preferably poly(vinyl acetate), grafted onto polyalkylene oxidebackbones. See European Patent Application 0 219 048, published Apr. 22,1987 by Kud, et al. Commercially available examples include SOKALANSRA's such as SOKALAN HP-22, available from BASF, Germany. Other SRA'sare polyesters with repeat units containing 10-15% by weight of ethyleneterephthalate together with 90-80% by weight of polyoxyethyleneterephthalate, derived from a polyoxyethylene glycol of averagemolecular weight 300-5,000. Commercial examples include ZELCON 5126 fromDupont and MILEASE T from ICI.

U.S. Pat. No. 5,415,807, Gosselink, Pan, Kellett and Hall, issued May16, 1995. Suitable monomers for the above SRA include Na2-(2-hydroxyethoxy)-ethanesulfonate, DMT, Na-dimethyl5-sulfoisophthalate, EG and PG.

Additional classes of SRA's include (I) nonionic terephthalates usingdiisocyanate coupling agents to link up polymeric ester structures, seeU.S. Pat. No. 4,201,824, Violland et al. and U.S. Pat. No. 4,240,918Lagasse et al; (II) SRA's with carboxylate terminal groups made byadding trimellitic anhydride to known SRA's to convert terminal hydroxylgroups to trimellitate esters. With a proper selection of catalyst, thetrimellitic anhydride forms linkages to the terminals of the polymerthrough an ester of the isolated carboxylic acid of trimelliticanhydride rather than by opening of the anhydride linkage. Eithernonionic or anionic SRA's may be used as starting materials as long asthey have hydroxyl terminal groups which may be esterified. See U.S.Pat. No. 4,525,524 Tung et al.; (III) anionic terephthalate-based SRA'sof the urethane-linked variety, see U.S. Pat. No. 4,201,824, Violland etal; (IV) poly(vinyl caprolactam) and related co-polymers with monomerssuch as vinyl pyrrolidone and/or dimethylaminoethyl methacrylate,including both nonionic and cationic polymers, see U.S. Pat. No.4,579,681, Ruppert et al.; (V) graft copolymers, in addition to theSOKALAN types from BASF made, by grafting acrylic monomers on tosulfonated polyesters; these SRA's assertedly have soil release andanti-redeposition activity similar to known cellulose ethers: see EP279,134 A, 1988, to Rhone-Poulenc Chemie; (VI) grafts of vinyl monomerssuch as acrylic acid and vinyl acetate on to proteins such as caseins,see EP 457,205 A to BASF (1991); (VII) polyester-polyamide SRA'sprepared by condensing adipic acid, caprolactam, and polyethyleneglycol, especially for treating polyamide fabrics, see Bevan et al, DE2,335,044 to Unilever N. V., 1974. Other useful SRA's are described inU.S. Pat. Nos. 4,240,918, 4,787,989, 4,525,524 and 4,877,896.

Brightener

Any optical brighteners or other brightening or whitening agents knownin the art can be incorporated at levels typically from about 0.01% toabout 1.2%, by weight, into the detergent compositions herein.Commercial optical brighteners which may be useful in the presentinvention can be classified into subgroups, which include, but are notnecessarily limited to, derivatives of stilbene, pyrazoline, coumarin,carboxylic acid, methinecyanines, dibenzothiophene-5,5-dioxide, azoles,5- and 6-membered-ring heterocycles, and other miscellaneous agents.Examples of such brighteners are disclosed in “The Production andApplication of Fluorescent Brightening Agents”, M. Zahradnik, Publishedby John Wiley & Sons, New York (1982).

Specific examples of optical brighteners which are useful in the presentcompositions are those identified in U.S. Pat. No. 4,790,856, issued toWixon on Dec. 13, 1988. These brighteners include the PHORWHITE seriesof brighteners from Verona. Other brighteners disclosed in thisreference include: Tinopal UNPA, Tinopal CBS and Tinopal 5BM; availablefrom Ciba-Geigy; Artic White CC and Artic White CWD, the2-(4-styryl-phenyl)-2H-naptho[1,2-d]triazoles;4,4′-bis-(1,2,3-triazol-2-yl)-stilbenes; 4,4′-bis(styryl)bisphenyls; andthe aminocoumarins. See also U.S. Pat. No. 3,646,015, issued Feb. 29,1972 to Hamilton.

Dye Transfer Inhibiting Agents

The compositions of the present invention may also include one or morematerials effective for inhibiting the transfer of dyes from one fabricto another during the cleaning process. Generally, such dye transferinhibiting agents include polyvinyl pyrrolidone polymers, polyamineN-oxide polymers, copolymers of N-vinyl-pyrrolidone andN-vinylimidazole, manganese phthalocyanine, peroxidases, and mixturesthereof. Preferred polyamine N-oxides are those wherein R is aheterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine,piperidine and derivatives thereof. If used, these agents typicallycomprise from about 0.01% to about 10% by weight of the composition,preferably from about 0.01% to about 5%, and more preferably from about0.05% to about 2%.

The N—O group can be represented by the following general structures:

The most preferred polyamine N-oxide useful in the detergentcompositions herein is poly(4-vinylpyridine-N-oxide) which as an averagemolecular weight of about 50,000 and an amine to amine N-oxide ratio ofabout 1:4.

Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers (referredto as a class as “PVPVI”) are also preferred for use herein. Preferablythe PVPVI has an average molecular weight range from 5,000 to 1,000,000,more preferably from 5,000 to 200,000, and most preferably from 10,000to 20,000. (The average molecular weight range is determined by lightscattering as described in Barth, et al., Chemical Analysis, Vol 113.“Modem Methods of Polymer Characterization”, the disclosures of whichare incorporated herein by reference.) The PVPVI copolymers typicallyhave a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1:1 to0.2:1, more preferably from 0.8:1 to 0.3:1, most preferably from 0.6:1to 0.4:1. These copolymers can be either linear or branched.

The present invention compositions also may employ apoly-vinyl-pyrrolidone (“PVP”) having an average molecular weight offrom about 5,000 to about 400,000, preferably from about 5,000 to about200,000, and more preferably from about 5,000 to about 50,000. PVP's areknown to persons skilled in the detergent field; see, for example,EP-A-262,897 and EP-A-256,696, incorporated herein by reference.Compositions containing PVP can also contain polyethylene glycol (“PEG”)having an average molecular weight from about 500 to about 100,000,preferably from about 1,000 to about 10,000. Preferably, the ratio ofPEG to PVP on a ppm basis delivered in wash solutions is from about 2:1to about 50:1, and more preferably from about 3:1 to about 10:1.

The detergent compositions herein may also optionally contain from about0.005% to 5% by weight of certain types of hydrophilic opticalbrighteners which also provide a dye transfer inhibition action. Ifused, the compositions herein will preferably comprise from about 0.01%to 1% by weight of such optical brighteners.

Particular brightener species, commercially marketed under thetradenames Tinopal-UNPA-GX, Tinopal AMS-GX, and Tinopal 5BM-GX byCiba-Geigy Corporation, are also included. Tinopal-UNPA-GX is thepreferred hydrophilic optical brightener useful in the detergentcompositions herein.

Suds Supressors

Suds suppression can be of particular importance in the so-called “highconcentration cleaning process” as described in U.S. Pat. No. 4,489,455and 4,489,574 and in front-loading European-style washing machines.

A wide variety of materials may be used as suds suppressors, and sudssuppressors are well known to those skilled in the art. See, forexample, Kirk Othmer Encyclopedia of Chemical Technology, Third Edition,Volume 7, pages 430-447 (John Wiley & Sons, Inc., 1979). One category ofsuds suppressor of particular interest encompasses monocarboxylic fattyacid and soluble salts therein. See U.S. Pat. No. 2,954,347, issued Sep.27, 1960 to Wayne St. John. The monocarboxylic fatty acids and saltsthereof used as suds suppressor typically have hydrocarbyl chains of 10to about 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitablesalts include the alkali metal salts such as sodium, potassium, andlithium salts, and ammonium and alkanolammonium salts.

The detergent compositions herein may also contain non-surfactant sudssuppressors. These include, for example: high molecular weighthydrocarbons such as paraffin, fatty acid esters (e.g., fatty acidtriglycerides), fatty acid esters of monovalent alcohols, aliphaticC₁₈-C₄₀ ketones (e.g., stearone), etc. Other suds inhibitors includeN-alkylated amino triazines such as tri- to hexa-alkylmelamines or di-to tetra-alkyldiamine chlortriazines formed as products of cyanuricchloride with two or three moles of a primary or secondary aminecontaining 1 to 24 carbon atoms, propylene oxide, and monostearylphosphates such as monostearyl alcohol phosphate ester and monostearyldi-alkali metal (e.g., K, Na, and Li) phosphates and phosphate esters.The hydrocarbons such as paraffin and haloparaffin can be utilized inliquid form. Hydrocarbon suds suppressors are described, for example, inU.S. Pat. No. 4,265,779, issued May 5, 1981 to Gandolfo et al.

Another preferred category of non-surfactant suds suppressors comprisessilicone suds suppressors. This category includes the use ofpolyorganosiloxane oils, such as polydimethyl-siloxane, dispersions oremulsions of polyorganosiloxane oils or resins, and combinations ofpolyorganosiloxane with silica particles wherein the polyorganosiloxaneis chemisorbed or fused onto the silica. Silicone suds suppressors arewell known in the art and are, for example, disclosed in U.S. Pat. No.4,265,779, issued May 5, 1981 to Gandolfo et al and European PatentApplication No. 89307851.9, published Feb. 7, 1990, by Starch, M. S.

Other silicone suds suppressors are disclosed in U.S. Pat. No. 3,455,839which relates to compositions and processes for defoaming aqueoussolutions by incorporating therein small amounts of polydimethylsiloxanefluids.

Mixtures of silicone and silanated silica are described, for instance,in German Patent Application DOS 2,124,526. Silicone defoamers and sudscontrolling agents in granular detergent compositions are disclosed inU.S. Pat. No. 3,933,672, Bartolotta et al, and in U.S. Pat. No.4,652,392, Baginski et al, issued Mar. 24, 1987.

Other suds suppressors useful herein comprise the secondary alcohols(e.g., 2-alkyl alkanols) and mixtures of such alcohols with siliconeoils, such as the silicones disclosed in U.S. Pat. Nos. 4,798,679,4,075,118 and EP 150,872. The secondary alcohols include the C₆-C₁₆alkyl alcohols having a C₁-C₁₆ chain. A preferred alcohol is 2-butyloctanol, which is available from Condea under the trademark ISOFOL 12.Mixtures of secondary alcohols are available under the trademarkISALCHEM 123 from Enichem. Mixed suds suppressors typically comprisemixtures of alcohol+silicone at a weight ratio of 1:5 to 5:1.

Alkoxylated Polycarboxylates

Alkoxylated polycarboxylates such as those prepared from polyacrylatesare useful herein to provide additional grease removal performance. Suchmaterials are described in WO 91/08281 and PCT 90/01815 at p. 4 et seq.,incorporated herein by reference. Chemically, these materials comprisepolyacrylates having one ethoxy side-chain per every 7-8 acrylate units.The side-chains are of the formula —(CH₂CH₂O)_(m)(CH₂)_(n)CH₃ wherein mis 2-3 and n is 6-12. The side-chains are ester-linked to thepolyacrylate “backbone” to provide a “comb” polymer type structure. Themolecular weight can vary, but is typically in the range of about 2000to about 50,000. Such alkoxylated polycarboxylates can comprise fromabout 0.05% to about 10%, by weight, of the compositions herein.

Fabric Softeners

Various through-the-wash fabric softeners, especially the impalpablesmectite clays of U.S. Pat. No. 4,062,647, Storm and Nirschl, issuedDec. 13, 1977, as well as other softener clays known in the art, canoptionally be used typically at levels of from about 0.5% to about 10%by weight in the present compositions to provide fabric softenerbenefits concurrently with fabric cleaning. Clay softeners can be usedin combination with amine and cationic softeners as disclosed, forexample, in U.S. Pat. No. 4,375,416, Crisp et al, Mar. 1, 1983 and U.S.Pat. No. 4,291,071, Harris et al, issued Sep. 22, 1981.

The compositions of this invention can be used to form aqueous washingsolutions for use in the laundering of fabrics. Generally, an effectiveamount of such compositions is added to water, preferably in aconventional fabric laundering automatic washing machine, to form suchaqueous laundering solutions. The aqueous washing solution so formed isthen contacted, preferably under agitation, with the fabrics to belaundered therewith.

An effective amount of the liquid detergent compositions herein added towater to form aqueous laundering solutions can comprise amountssufficient to form from about 500 to 7,000 ppm of composition in aqueoussolution. More preferably, from about 800 to 3,000 ppm of the detergentcompositions herein will be provided in aqueous washing solution.

The following examples are illustrative of the present invention, butare not meant to limit or otherwise define its scope. All parts,percentages and ratios used herein are expressed as percent weightunless otherwise specified.

In the following Examples all levels are quoted as % by weight of thecomposition.

EXAMPLE I

The following non-limiting examples are within the scope of the presentinvention.

Example A B C D E F G H I J K L M C12-15E2.5S 21 21 20.2 22.7 22.7 13.618.12 18.25 22.65 22.65 27.65 22.65 22.65 C12LAS — — — — — 9.1 4.5 — — —C12-14 glucosamide 4 4 2.5 — — — C12-14EO7 4.5 4.5 — — — C12-15EO9 — —0.6 0.6 0.6 0.6 0.6 5 0.6 0.6 0.6 0.6 0.6 C8-10 amidopropylamine 1.3 1.3— — — C10 amidopropylamine — — 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.31.3 citric acid 1 3 5 1 2.5 1 1 1 1 1 1 1 1 C12/14 fatty acid — — 10 108 10 10 10 10 10 7.5 5 10 Quaternary Surfactant 0.5 1 5 — oleic acid — —— 2.5 palm kernal fatty acid 8 5.4 — — — — rapeseed fatty acid 8 5.4 — —— — protease 0.6 0.6 0.9 0.9 0.9 0.9 0.9 0.9 0.9 0.9 0.9 0.9 0.9 lipase0.07 0.07 0.08 0.08 0.08 0.08 0.08 0.08 0.08 0.08 0.08 0.08 0.08 amylase0.18 0.18 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15cellulase 0.03 0.03 0.05 0.05 0.05 0.05 0.05 0.05 0.05 endolase 0.2 0.2— — — — 0.05 0.05 0.05 0.05 brightener 0.15 0.15 0.15 0.15 0.15 0.150.15 0.15 0.15 0.15 0.15 0.15 0.15 polymer A 0.66 0.66 0.6 0.6 0.6 0.60.6 0.6 0.3 0.6 0.6 0.6 0.6 polymer B — — 1.2 1.2 1.2 1.2 1.2 1.2 0.61.2 1.2 1.2 1.2 Polyamine-polyamide 2 — 1 1 — — Polyethoxylated- — 1 2 —— — polyamines soil release agent — — 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.10.1 0.1 0.1 ethanol 0.7 0.7 0.54 0.54 0.54 0.54 0.54 0.54 0.54 0.54 0.540.54 0.54 1,2-propanediol 4 4 4 4 4 4 4 4 4 4 4 4 4 MEA 0.7 0.7 0.5 0.50.5 0.5 0.48 0.48 0.48 0.48 0.48 0.48 0.48 NaOH 2.8 2.8 7 7 7 7 7 7 7 77 7 7 boric acid 2 2 — — — — borax — — 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.52.5 — 2.5 suds supressor — — 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1PDMS 0.2 0.2 — — — — perfume 0.5 0.5 0.75 0.75 0.75 0.75 0.75 0.75 0.750.75 0.75 0.75 0.75 dye — — 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.04 0.040.04 0.04 water balance balance balance balance balance balance balancebalance balance balance balance balance balance Polymer A are modifiedpolyamines of PEI (MW = 182) with average degree of ehtoxylation = 15Polymer B are modified polyamines of PEI (MW = 600) with average degreeof ethoxylation = 20 Monoethanolamine = (MEA)

Quaternary Surfactant is selected from one or more of the following:lauryl trimethyl ammonium chloride, myristyl trimethyl ammoniumchloride, palmityl trimethyl ammonium chloride, coconuttrimethylammonium chloride, coconut trimethylammonium methylsulfate,coconut dimethyl-monohydroxyethyl-ammonium chloride, coconutdimethyl-monohydroxyethylammonium methylsulfate, steryldimethyl-monohydroxy-ethylammonium chloride, steryldimethylmonohydroxy-ethylammonium methylsulfate, di-C₁₂-C₁₄ alkyldimethyl ammonium chloride.

The polyamide-polyamines herein are commercially marketed under thetradenames: Kymene®, Kymene 557H®, Kymene 557LX®, Reten®, andCartaretin®.

What is claimed is:
 1. A gel laundry detergent composition comprising byweight of the composition: a) from 15% to 40% of an anionic surfactantcomponent wherein anionic surfactant component comprises, by weight ofthe composition; (i) from about 5% to about 25% of alkyl polyethoxylatesulfates wherein the alkyl group contains from about 10 to about 22carbon atoms and the polyethoxylate chain contains from about 0.5 toabout 15 ethylene oxide moieties; and (ii) from about 5% to about 20% offatty acids; b) a detersive amine; c) from 0% to 4.7% by weight of thecomposition of total organic solvent; and wherein said composition has aviscosity of from about 100 cp to about 4,000 cp at 20 s⁻¹ shear rate.2. A composition according to claim 1 wherein the detergent compositionadditionally comprises adjunct ingredients selected from the groupconsisting of non-citrate builders, optical brighteners, soil releasepolymers, dye transfer inhibitors, polymeric dispersing agents, enzymes,suds suppressers, dyes, perfumes, colorants, filler salts, hydrotropes,antiredeposition agents, antifading agent, dye fixative agents,prill/fuzzing reducing agents, and mixtures thereof.
 3. A compositionaccording to claim 1 wherein the ingredient (b) comprises from about0.1% to about 10%, by weight, of a detersive amine; wherein said amineis of the formula:

wherein R₁ is a C₆-C₁₂ alkyl group; n is from about 2 to about 4, X is abridging group which is selected from NH, CONH, COO, or O or X can beabsent; and R₃ and R₄ are individually selected from H, C₁-C₄ alkyl, or(CH₂—CH₂—O(R₅)) wherein R₅ is H or methyl.
 4. A composition according toclaim 3 wherein the detersive amine is selected from the groupconsisting of: octyl amine, hexyl amine, decyl amine, dodecyl amine,C₈-C₁₂ bis(hydroxyethyl)amine, C₈-C₁₂ bis(hydroxyisopropyl)amine, C₈-C₁₂amido-propyl dimethyl amine and mixtures thereof.
 5. A compositionaccording to claim 4 wherein said detersive amine comprises C₈-C₁₂amido-propyl dimethyl amine.